We present a comprehensive study on the diphosphanation of iso(thio)cyanates by unsymmetrical diphosphanes. The reactions involving unsymmetrical diphosphanes and phenyl isocyanate or phenyl thioisocyanate gave rise to phosphanyl, phosphoryl, and thiophosphoryl derivatives of amides, imines, and iminoamides. The structures of the diphosphanation products were confirmed through NMR spectroscopy, IR spectroscopy, and single-crystal X-ray diffraction. We showed that unsymmetrical diphosphanes could be used as building blocks to synthesize phosphorus analogues of important classes of organic molecules. The described transformations provided a new methodology for the synthesis of organophosphorus compounds bearing phosphanyl, phosphoryl, or thiophosphoryl functional groups. Moreover, theoretical studies on diphosphanation reactions explained the influence of the steric and electronic properties of the parent diphosphanes on the structures of the diphosphanation products.

中文翻译：

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探索不对称二膦对杂聚烯的反应性：获取酰胺、亚胺和亚氨基酰胺的磷酰基和磷酰基衍生物

我们对不对称二膦对异（硫）氰酸酯的二膦化进行了综合研究。涉及不对称二膦和异氰酸苯酯或硫代异氰酸苯酯的反应产生酰胺、亚胺和亚氨基酰胺的磷酰基、磷酰基和硫代磷酰基衍生物。通过 NMR 光谱、IR 光谱和单晶 X 射线衍射证实了二磷化产物的结构。我们表明，不对称二膦可用作合成重要有机分子类别的磷类似物的构件。所描述的转化为合成带有磷酰基、磷酰基或硫代磷酰基官能团的有机磷化合物提供了一种新的方法。而且，